Distortion Isomerism of Cu(II) Chloride Adducts with Bis(2-benzimidazolyl)ethane. Synthesis, Characterization, X-ray Structures and Spectroscopy of Four Different Isomers

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• 作者：Gerard A. van Albada ; Ilpo Mutikainen ; Urho Turpeinen and Jan Reedijk
• 关键词：Copper(II) ; Plasticity effect ; Crystal structure ; Distortion isomerism ; Hydrogen bonding
• 刊名：Journal of Chemical Crystallography
• 出版年：2007
• 出版时间：July, 2007
• 年：2007
• 卷：37
• 期：7
• 页码：489-496
• 全文大小：262 KB
• 刊物类别：Chemistry and Materials Science
• 刊物主题：Chemistry
  Organometallic Chemistry
  Crystallography
  Physical Chemistry
  Inorganic Chemistry
  
• 出版者：Springer Netherlands
• ISSN：1572-8854

文摘

3D structures and spectroscopic properties are reported of four compounds with the ligand bis(2-benzimidazolyl)ethane (hereafter abbreviated as dbz) attached to CuCl₂, all having the general formula [Cu(dbz)Cl₂](Hb) _x . (in which Hb = EtOH or MeOH and x = 1/2 or 1). The X-ray crystal structure has been solved from these four slightly different compounds, namely: green α-[CuCl₂dbz](C₂H₅OH)_1/2 (1), the red compound β-[CuCl₂dbz](C₂H₅OH)_1/2 (2), which both have two slightly different units in the unit cell, the red α-[CuCl₂dbz](CH₃OH) (3) and a blue–green compound β-[CuCl₂dbz](CH₃OH) (4). The geometry around the Cu(II) anion is distorted tetrahedral for all four compounds, with chromophores consisting of two nitrogen atoms of the bidentate chelating dbz molecule and two chloride anions. The unit cells of compound 1 and 2 consist of two chemically identical, but crystallographically different units, while compounds 3 and 4 each have only one independent CuCl₂-(dbz) unit. The major differences are observed in the dihedral angles NCuN–ClCuCl, which vary from 29.3 to 77.1° for the four compounds. The differences are related to different packing effects, ring–ring stacking and H-bond interaction, due to the two different alcohols used. In fact these four compounds represent a new range of examples of distortion isomerism in pseudo-tetrahedrally coordinated species. Characterisation of the four compounds has been completed by IR, EPR and LF spectroscopy.